PT87645B - PROCESS FOR THE PREPARATION OF FUNGICID COMPOSITIONS CONTAINING SYNERGIC MIXTURES OF QUATERNARY AMMONIUM COMPOUNDS WITH IODOPROPYLLOXY-ETHANOL-CARBAMATE COMPOUNDS - Google Patents

Description

The invention relates to mixtures of substances

active fungicides, in particular, to anti-microbially active mixtures with a content of quaternary ammonium compounds and iodopropynyloxy-ethanol-carbamate compounds.

The use of quaternary ammonium halides as an active substance in anti-microbial agents, has been known for a long time, see for example, K. Lindner Surfactants, textile auxiliary-detergent materials pg. 984, 24th. edition, vol. 1, publisher Wissenschaftlische See lagsgesellschaft mbH, Stuttgart, and Kirk-Othmer, “Encyclopedia of Chemical Technology, p. 530, 3 · edition, vol. 19, John Wiley & Sons publisher, New York, Chichester, Brisbane, Toronto, Singapore. Also, the use of io ·· dopropynyloxy-ethanol carbamates as bactericides and fungicides has been practiced for a long time; see for example the German Patent of 32 16 895 A1.

In the field of disinfection and conservation agents> and from the point of view of protecting the environment and also the economy, there is a need for active substances and combinations of active substances that have satisfactory anti-microbial results even when applied in low concentration . In this context, not only are new compounds of interest, but also combinations of synergistic effects of active substances already known.

It has been discovered that combinations of benzalkonium-type quaternary ammonium halides with iodopropynyloxyethanol carbamates show synergistic anti-microbial effects, when both components exist in a certain weight ratio between them.

The object of the invention is antimicrobial active mixtures containing:

a) at least one quaternary ammonium compound with anti-microbial effect and t

b) at least one iodopropynyl oxy-ethanol carbamate compound, with anti-microbial effect, in which components a and b are in a weight ratio of a: b ranging from 0.3: 1 to 9: 1 «

For this purpose, anti-microbial quaternary ammonium compounds, substances of the benzalkonium type that correspond to the formula I (CH ₃ ) ₂ J Χθ (I) are especially of interest

2 in which R and R can be the same or different and preferably represent a straight chain alkyl radical with 8 to 18 carbon atoms or a benzyl radical, and Χθ represents a halogen anion, especially a chloride anion and

2 wherein only one of the radicals R or R can be a benzyl radical. These quaternary ammonium compounds may, in the mixtures according to the invention, be contained in the form of single compounds or mixtures. Examples of such quaternary ammonium compounds with antimicrobial effect are benzyl-dimethyl-n-decylammonium chloride, benzyl-dimethyl-n-dodecylammonium chloride, benzyl-dimethyl-n-tetradecylammonium chloride, benzyl-dimethyl-n-chloride octadecylammonium and benzyl-dimethyl-cocoalkylammonium chloride, in which the radical S of formula I is derived from the hydrogenated fatty acid mixture of coconut oil, as well as dioctyldimethyl-dimethylammonium chloride and didecyl-dimethylammonium chloride. Benzyl-dimethyl-n-dodecylammonium chloride and benzyl-dimethyl-n-tetradecylammonium chloride are preferred, as are mixtures of these compounds.

Iodopropynyloxy-ethanol-carbamate compounds, with anti-microbial effect, are particularly suitable. 2- (J-iodo-propynyloxy) -ethanol-carbamates of general formula II

- 4 R ⁵ R ⁵

I - GbC- C -0- C -C -0C0NH -R '(II)' 6 R R

2 in which R and R are the same or different and mean hydrogen, linear or branched alkyl or alkenyl radicals with 1 to 6 carbon atoms, or cycloalkyl radicals with 5 to 7 carbon atoms, or R and R together mean (0Η ₂ ) „» Where n is a number from 4 to 6, en '

R ⁵ , cg

Ir and R are the same or different and mean hydrogen, alkyl radicals with 1 to 4 carbon atoms, radi chg aryl or CCl ^, or R ⁹ and R ⁹ or R and R together signify (Oí ^ n ' ⁱⁿ ^ ^{eu 11} ® ¹¹²¹¹ number 3 to 5 »e / means hydrogen, straight or branched alkyl radicals having 1 to 12 carbon atoms or cycloalkyl radicals having 4 to 8 carbon atoms, aryl radicals, substituted ar radicals, radicals alkyl or arylsulfonyl radicals

Examples of straight or branched alkyl or alkenyl radicals having 1 to 6 carbon atoms, corresponding to R and R, are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tertiary groups. butyl, pentyl hexyl, and its branched isomers, vinyl, allyl, propenyl, pentenyl and hexenyl, as well as the respective isomers of the mentioned alkenyl radicals with 4, 5 and 6 carbon atoms.

Examples of cyclic alkyl radicals having 5 to 12 carbon atoms, corresponding to R and R, are the radicals derived from cyclopentane, cyclohexane and cycloheptane.

Preferred are the compounds of the formula (ΣΙ) in which 2 both R and R substituents may be hydrogen or methyl at the same time as those in which R 1 and R 1, one represents hydrogen, while the other represents methyl.

Examples of alkyl radicals with 1 to 4 atoms of

4 5 6 carbon, represented by R, R, ir and R, the methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl groups, where the methyl radical is preferred.

Examples of aryl radicals, represented by 3 4 5 6

R, R, R and R are phenyl and naphthyl groups.

Preferred are compounds of the general formula 16 (II), in which of the radicals R to R, at least 4 signify hydrogen.

Examples of linear alkyl or branched radicals having 1 to 12 carbon atoms represented by R 'are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, tert.-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, as well as branched isomers of alkyl groups with 5 to 12 carbon atoms.

Examples of cyclic alkyl radicals having 4 to 8 carbon atoms, represented by R ?, are the cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups.

Examples are aryl and substituted aryl, represented by R, the phenyl, naphthyl, tolyl, chlorophenyl, bromophenyl, fluorophenyl, dichlorophenyl and trichlorophenyl groups.

Examples of aralkyl and arylsulfonyl radicals, 7 represented by R, are benzyl and p-toluenesulfonyl groups.

Compounds in which R? is a lower alkyl radical with 1 to 4 carbon atoms, as well as an unsubstituted aryl radical or an aryl radical substituted by chlorine or bromine.

Examples of especially preferred compounds are those in the current TS? Q is propyl, butyl or phenyl.

The substituted 2- (3-iodo-2-propynyloxy) -ethanol-carbamates of the general formula (II) are synthesized according to known processes (Houben-Weyl, Methoden der Org. Cho mie ”, Bd. 8, pp. 141 to 144 (1952)), by reacting equimolar quantities of alcohol with for example suitable isocyanates, which can be obtained commercially, as described in the descriptions of German Patents Nos. DE 32 16 894 A1 and DE 32 16 895 Al.

By determining the microbiostatic effect in different cultures of fungi, it was possible to observe with these mixtures evident synergistic effects.

According to a preferred embodiment of the present invention, the weight ratio of components a) and b) is between 1: 1 and 6: 1.

For the preparation of an anti-microbial composition in ready-to-use form, mixtures with an anti-microbial effect according to the invention may be prepared in the form of aqueous concentrates, in which the total concentration of components a) and b) can be comprised between 5 β and 50% by weight. In aqueous antimicrobial agents ready for use, such as those intended for disinfectant or preservation purposes, the total concentration of components a) and b) is generally between 0,005 β os% by weight in relation to the totality of the agent.

Mixtures with microbial effect ready for use consist, in the simplest cases, of an aqueous solution, in which the quaternary ammonium compound and the iodopropynyloxy-ethanol-carbamate compound are dissolved in the indicated proportion and concentration. In most cases, certain mixtures for practical application normally contain

other currently usable components, which are chosen according to the intended use and the purpose of that use. For liquid formulations, not only water, but also mixtures of water and organic solvents that can be mixed with water, such as ethanol, isopropanol, ethylene glycol, propylene glycol, ethyl ethylene glycol and propylene propylene, are of interest as water dissolving agents. These solutions are easily sprayable, using either compressed air or a common entraining agent used in aerosol techniques for the production of sprays.

When, in addition to having an anti-microbial effect, it is also desired to obtain an additional detergent effect, the mixtures according to the invention may contain surfactants, in particular suitable surfactants are addition products of 4 to 10 moles , preferably 4 to 20 moles, of ethylene oxide to one mole of fatty alcohol, alkylcyclohexanol, alkylphenol, fatty acid, fatty amine, fatty acid amide or alkanesulfonamide. Of particular interest are products of addition of 5 to 16 moles of ethylene oxide and fatty alcohols of coconut or tallow, oleyl alcohol, a mixture of allylic alcohol and cetyl alcohol, as well as mono-, di- or trialkylphenols and monoalkylcyclohexanols with 6 to 14 carbon atoms in the alkyl radicals. Also of interest are products of addition of mixtures of ethylene oxide and propylene oxide to said compounds with an active hydrogen atom. The aforementioned alkoxylation products can be closed with groups at the ends, for example, by ether and acetal groups.

In the mixtures according to the invention, in addition, there may also be bulking auxiliary substances. For this purpose, for example, alkali metal salts of glucenic acid, especially sodium gluconate, alkali metal salts of nitrilacetic acid, ethyl

lenodiamintetracético, hydroxyethanodiphosphonic acid, phosphonobutanotricarboxylic acid, lactic acid, citric acid hi. tertic acid. Also of interest as bulking auxiliary substances are water-soluble salts of high molecular weight polycarboxyl acids, such as polymers of maleic acid, itaconic acid, fumaric acid and citraconic acid. Also, the copolymers of these acids with each other or with other polymerizable monomers such as ethylene, propylene, acrylic acid, vinyl acetate are usable with isobutylene, acrylamide and styrene.

In the mixtures according to the present invention, cleaning reinforcing agents, such as monetanolamides and fatty acid diethanolamides, for example, monoethanol, coconut fatty acid amide and coconut fatty acid diethanolamide and products for adding up to 4 moles of ethylene oxide or propylene oxide, to alkolines with 12 to 18 carbon atoms or to fatty alcohols with 8 to 12 carbon atoms and free fatty alcohols with 8 to 12 carbon atoms, as well as cellulose-based cleaners.

In addition, it can be advantageous for other fields of application, than mixtures according to the present invex. contain other substances with antimicrobial effect, added to the combination of quaternary ammonium compounds with iodopropynyloxyethanol-carbamate compounds.

I

For the preparation of ready-to-use detergent solutions with disinfectant effects, solid products can also be prepared, in addition to liquid concentrates, preferably in the form of powder or granules, containing the active anti-microbial mixture according to the invention. .

Mixtures with synergistic antimicrobial effect

they can be used successfully as disinfecting and preserving agents in many fields, such as surface disinfection in hospitals, schools, changing rooms, public transport and industrial companies and facilities. The mixtures according to the present invention have an important significance in the field of disinfection in agricultural companies, in dairy plants or beer plants, as well as in other companies in the food or beverage industry. Synergistic mixtures can also be used to conserve material for the production of plants, especially seeds and bulbs. They can also be used in the conservation of technical products such as dispersions of dyestuffs, adhesives, drilling and cutting oils, the products of the paper, cardboard and leather processing industries, as well as in the conservation of industrial and domestic water. Finally, the mixtures according to the present invention can be applied in the protection of materials for example in the impregnation of wood. In this case, for example, the boxes used in the industrial mushroom culture can thus be protected from attacks by the culture mycelium.

Examples

Example 1

From benzyl-dimethyl-n-dodecyl / n-tetradecylammonium (70 mol% in C] _2 'molar in 0 ^ 5 Product A) and 2- (3-iodopropynyl-oxy-ethanol-N-ethyl) carbamate Product Β), the following solutions were produced according to the invention: (Products C and D):

Product C (ratio A: B »4.5: 1)

Product D (ratio A; B * 1: 1)

The microbiostatic effectiveness of the mixtures according to the invention (Products C and I) compared to those of the individual components benzyl-dimethyl-n-dodecyl / n-tetradecylammonium chloride (Product A) and 2- (3-iodopropynyloxy carbamate) ) -ethanol-N-ethyl (Product B) was determined for the following suspensions of microorganisms:

1. Candida Albicans

2. Penicillium camerunense

3. Penicillium funiculosum

4. Trichoderma viride 5 · Aspergillus niger x 10 germ without ml 7 x 10 'germs / ml x 10' germ without ml

Q χ 10 ⁷ germs / ml x 10? germs / ml

The inhibitory concentrations of the substances and mixtures of substances examined were determined according to the recommendations for Examination and Evaluation of Chemical Disinfection Processes, ch. 2.1, printed in Zbl. Bakt. Hyg., Section I B 172, 536-537 (1981) · In all microorganisms the concentrations of active substances were (in ppm.): 20; 15; 10; 7; 4.5; 3; 2; 1.5, and 1.

The concentration series was prepared in a wort broth.

The results obtained are shown in the following table.

TABLE I

Inhibitory concentrations (in ppm) of Products A to D

Product 1 Mi crorgani smo s 2 3 rehearsed 4 5 THE 70 45 4.5 15 70 B 20 7 7 10 10 Ç 37 8.5 5.5 5.5 55 D 14 4 3 4 9

A synergistic effect can be observed with the application of Products C and D according to the invention. Sinergét: co in the sense of the present invention means the designation dii ed to the effect, when in a combination of both componentsen less than half of the minimum inhibitory concentration (MIC) is required.

In the table for the inhibitory concentration of the C and D products, the sum of both individual components, used in the proportions mentioned above, was indicated.

Claims (4)

CLAIMS: there. - Process for the preparation of fungicidal compositions containing synergistic mixtures of quaternary ammonium compounds with iodopropynyloxy-ethanol-carbamate compounds with anti-microbial effect, characterized by the fact that it is mixed a) at least one quaternary ammonium compound with anti-microbial effect with b) at least one iodopropynyloxy-ethanol-carbamate compound with anti-microbial effect, in a weight ratio between components a) and b) preferably comprised between about 0.3: 1 θ 9: 1 and the mixture thus obtained the appropriate carrier (s), diluents and / or auxiliaries are added in such a way that the amount of the active substance mixture is preferably between about 3 θ 50 percent by weight in the case of concentrates and between about from 0.005 and 5 percent by weight in the case of compositions which are for use. 2a. Process for preparing compositions with anti-microbial effect according to claim 1, characterized in that the components a) and b) are used in a weight ratio of a: b between 1: 1 and 6: 1 . 3a. Process for the preparation of compositions with anti-microbial effect according to claim 1 or 2, characterized in that, as quaternary ammonium compounds, substances having the formula (I) are used A ² n © (ch ₅ ) ₂ (I) 1 2 in which R and R can be the same or different and represent an alkyl radical having 8 to 18 carbon atoms preferably with the straight chain or a benzyl radical, and Χθ represents a halide anion, preferably a straight chloride anion, wherein only one of the radicals R or R can be a radical benzyl. 4th. Process for the preparation of compositions with anti-microbial effect, according to claims 1 to 3, characterized in that as a quaternary ammonium compound with anti-microbial effect, benzyl-dimethyl-n-dodecylammonium chloride, chloride is used benzyl-dimethyl-n-tetradecylammonium or mixtures of these compounds. Process for the preparation of compositions with anti-microbial effect, according to claims 1 to 4, characterized in that, as compounds of iodopropynyloxy-ethanol-carbamate with anti-microbial effect, substances corresponding to the formula (II ). R OCOHH - E ⁷ (II) 1 2 in which R and R are Equal or different, and mean hydrogen, linear or branched alkyl or alkenyl radicals with 1 to 6 carbon atoms, or cyclic alkyl radicals with 5 to 7 carbon atoms, or R and R together mean that n is a number 4 to 6, 3 4 5 6 R, R, R and R, which can be the same or different, mean hydrogen, alkyl radicals with 1 to 4 carbon atoms, aryl radicals or CCl ^, or R and R ^ or R and R together mean (0 ^ 2 ^ θπ which n is a number from 3 to 5, and R 'means hydrogen, linear alkyl radicals or ramieΛ - 14 with 1 to 12 carbon atoms, or cyclic alkyl radicals with 4 to 8 carbon atoms, unsubstituted aryl radicals, substituted aryl radicals, aralkyl radicals or arylsulfonyl radicals. 65. Process for the preparation of compositions with anti-microbial effect according to claims 1 to 5, characterized in that they are given the form of aqueous concentrates with a total concentration of components a) and b) between 5 and 50% by weight on the whole of the concentrate. 75. Process for the preparation of compositions with anti-microbial effect, according to claims 1 to 6, characterized in that they are given the form of ready-to-use anti-myerobial formulations containing water, with a total concentration of components a) and b) between 0.005 and 5% ^by weight in relation to the entire formulation. 85. - Stable disinfection process, characterized by the application of an anti-microbial composition containing a synergistic mixture of at least one compound of the formula, (I) with a compound of the formula (II) according to any of the claims 1 to 7, preferably with a concentration comprised between about 0.005 ® 5% by weight of active ingredients.